Fungicidal composition



Unt ed SW Pets? Offi 3,645,188 Patented July FUNGICIDAL COMPOSITION.

s tart fia tl ana f otsam li t hw t ntari Canada, and Gunter Goezc,Koin-Bayenthal, Gcr napy Fahlherg-Lint G.:t1.b.!-l. ,Chemischc Fahrilt,Gflllldt llat1. 1],Posfiaehl tfl, Wolfenbu'tttgl, Germany) "Noprayving'.Filed July 27,1959, seam). 829,505

' If-Claims. "(Gl.167--14) i --'"I h'isinvention-relates toimprovements'in the"composition'of- -'fungicidal' preparations effectivein protecting plants-"agat't'tst diseus'essuch as Phytophlhora,Fu'sicladium Oercospora, Perono'spor'a and the like. More particularlyit relates-to-improvements in fttgicidai composi' tions in which theconstituents imparting, fungicidal properties are copper compoundssupplemented by specific zinc compounds whichp roduce a synergisticeffect so that the resulting composition possesses fungicidal propertiesgreatly in excess of those attributable to the use of simi-' lar amountsof copper compounds and zinc compound sep arately.

It is well known that protection against diseases of the groups listedabove may be obtained by using copper compounds; When, howeven thismethod is used the quantity'of coppercompounds' necessary for aneffective protection of fields of some acreage is prodigious. For in--stance, in actual'pra'cticcithas been found that the amount of afo'ppercompound necessary to keep a potato field free of"Phytophthora,"spraycdonly once is between 2.5 and 5.0 kg.of cupric oxychloride or l.2 and 2.4kg. of'cup'rous oxide for'an acreage of one hectare (2.417 acres).

' It is well known that ziin'c cor'n'pounds do not possess anynoticeable fungicide properties in thetnirelvesfl However, prior effortsto dimnish the amount of copper compounds necessary to effectivelyprotect the plants from diseases mentioned above have included proposalsto use acombination of zinc or zinc compounds with copper compounds in"order to produce effective parasiticidcs.

One such proposal has been to dissolve copper and zinc salts in waterand to produce by means of alkaline matetials precipitateswhich aresoluble to a small extent only. According to this proposition, aprotective sub stance is formed which consists of a combination of basiccopper and zinc sulphate. This composition, according to its 'author issaid to have a synergistic effect and to pro duce a saving of copper upto 50%.

However various patents relating to this subject matter indicate thatany suchsynergistic effect is not the general -rule,,but rather theexception, notod only with specific combinationsof zinc and coppercompounds, and not with most combinations. For instance, in US. Patent1,905,532 it is stated that soluble zin'c compounds damage the foliageof solanaceous plants andthe use .of basiccopper and zinc sulphate isproposed as a fungi'eide, hydratcd lime being added toreduc'e' thedamage to the foliage. There is no mentiot't'of a synergistic effect andthe mixture is proposed to prevent ihe'damaging effect of zinc sulphate.per so. on the plants. 1

Another proposal is set forth in US. Patent 2.051910 wherein 'thephysicahproperties of copper silicate fungicides are said to be improvcdby replacing a portion of thezcopperwith zine; Lower damage to thefoliage was noted without a noticeable impairment in toxicity. 2-.lnUIS. Patent'2;225,867 a specific synergistic effect is noted when zineoxide'is used in combination with copper oxide; which is not evident inthe case of'othcr compounds, according to the patcntee. indeed in othercombinations, the patentee reported that the use of zinccompottnds-actuallydocrcased the effectiveness of the product.

The atents; further n'ogtes j that' when other com; pounds such ajs zinccarbonate, zines-names; "gincottala tc were used plac eof iinc iotiide,tho result-s ,w'pr nerciy additiveandno synergistic effe'c tfcoiuldbefound. 11 In stillanqther. US. Patent 2,540,209itfisstafeditl'iaizirtc s uifitejis .the only 'zinc salt 'whiehlig ive s' the desiredprotection against copper injury in coppcrfuogicides i s ,b f flt m-hi5. z

In summary then,. prior patents in'thisfie ld would ite nd to indicatethat it is by no means recognized that cop; per and zinccompounds .irgeneral, when used ;in.-com bination, produce synergistic effects, andlhatone prevail ing view is that .a huge number OfliItC compounds canonly be used if they canbe converted to basiccornpounds.

According to the present invcntiotra marked improve; ment in theeffectiveness offungicidcscopper compounds over the improvementspreviously reported is obtained by the use of zinc chromate and/orzincsulphide in adnti t tut'e \vithtungicide copper compounds.

Specifically it has been found that the amount of-cop: per compounds,.such as cuprous. oxide,' copper-oxychloride, basic copper carbonate,and ,the, lik e may be re; duced by as much as 75% whcn uscd with theproper proportions of the zinc compounds specified.

Thus in the prior art above noted, the besureported results amounted toa saving of 50% of copper w,hc n,a -c om; bination of a basiccopper-zinc .sulphate is. uscd,,when compared with the action of aqoppcr-sul-phate-limemlution. Howevcr,,wo have found that with asttitttble ww per compound used in combination with zinc sulphide orzinc chromate, an unexpectedly high saving with respect to the coppercompound is obtained and that only about one-fourth of the amount ofcopper compound heretofore deemed necessary need actually be used toeffectively control the diseases mentioned.

For instance, if a copper sulphate solution with 0.75% of coppersulphate is used in order to keep p tato fields free of Phytophthora, itis necessary. according to'the accepted practice, to use about-600liters for treutingnne hectare (2.417 acres) in order to treat .theplants. uniformly. it is therefore. necessary to expendfor each hcctare, 4.5 kg. of copper sulphate, a figure which corresponds to 1.8 kg.of metallic copper.

However, if according to the invention-n-cotnbination of for instance,copper oxychloride and zinc sulphide is used, actual field tests haveproved that/for each hectare only 600 goof copper oxychloride must beused which con tains 350 g. of metallic copper, Thisis clettrlyan effectwhich could not have been foreseen. The savings thus obtained are aboutfottr times the savings obtainable by the best method of saving so farmentioned in the literature above quoted. The savings are still greaterif compared with those plant protection compoundsand. mixturcs wbich arenow used and which hnv bcon endorsed officially byGovernmentuuthoritics. One of these-rec ognizcd spraying meanscontaining copperguses 2.5 kg. of copper oxychloride witlna content of1445 kg. ofcoppor metal-for each hectare sprayed.v This is-the bcst'compound now known whichhasfound general rocogx'ttn'om Therefore, whencompared with the most modernzooppot spraying fungicide the combinationaccording to thc in'v'ention has the advarnage that -ituses..only-oheifourth -of the copper or, otherwise stated, that aquantity equal to three times the quantity actually used can beconsidered as having been saved. I

A further advantage. of -thb tnvention'consists in lhe fact thatthe-rather cumbersome convcrsioh of the and zinc compounds into theirbasic stilts by m'eans of substances of alkaline reaction can bedispensed with. j A further advantage of the combination consists in thefact that no damage to the foliage results, even if the aces, 188

dosage should for some reason or other be excessive. While applicants donot want to advance any theory for this increased elfectiveness, theyassume that zinc chromate as well as Zinc sulphide activate the coppercompounds to a high degree. This has been deduced from experiments withother zinc compounds (e.g. with zinc carbonate) which do not produce anyincrease in the effectiveness of the copper salts as a fungicide.

Before illustrating this invention in the specific examples whichfollow, certain limiting and critical featuresdust or spray is to beapplied. The relative proportions of zinc compound: copper compound inthe mixture should preferably be between 1:4 and 1:8; that is, for everyfive parts by weight of zinc compound, between 20 and 40 parts by weightof a suitable copper fungicide should be present.

(4) Other ingredients which may be present in the composition includediluents commonly used in the preparation of sprays, pastes or dusts.

The examples which follow are intended to be taken as illustrative ofthe invention and not as limitative.

Example 1.Spraying Powder [Proportions in grams] g. copper oxychloride,and 5 g. zinc chromate are intimately mixed with 55 g. kaolin. In thismixture 5 g. of a higher molecular weight aliphatic sulfonic acid actingas a wetting agent and as an emulsifier such as sodium sulforicinate and10 g. of an adhesive known as cell powder are worked.

A suspension of 3 kg. of a mixture, prepared with the above proportionsindicated in grams, in 600 liters of water is prepared. This quantity issprayed uniformly on each hectare of a potato field.

In an experimental test the potato plants on a ground parcel Weretreated and those on an adjacent ground parcel were not treated byspraying. On the non-treated section the plants on account ofinfestation with Phytophthora died, on the sprayed section the plantsremained healthy and completely free of Phytophthora.

Example 2.S praying Paste [Proportions in grams] g. copper oxychlorideand 5 g. zinc sulphide are stirred and intimately and thoroughly mixedby agitation with 25 g. of a watery dispersion of polyvinylacetate, 0.5g. animal glue powder, the latter acting as a stabilizer, and 39.5 g. ofwater.

The mix has the consistency of a paste and 3 kg. of this paste aresuspended in 600 liters of water. This quantity is sprayed on onehectare (2.417 acres) of potato plants.

The experiment mentioned in Example 1, was also made with this mixtureof Example 2.

Example 3.Spraying Paste [Proportions in grams] The same effect as thatdescribed in Examples 1 and 2 is obtained with a mix of 22 g. cuprousoxide, 5 g. zinc sulphide, 25 g. of a watery dispersion of polyvinylpropionate, 0.5 g. of animal glue serving as a stabilizer, and 47.5 g.of water which are intimately mixed to form a paste. 3 kg. of the pastesuspended in 600 liters of water 4 are again the quantity sprayed foreach hectare of a potato field.

Example 4.-Spraying Paste [Proportions in grams] 30 g. copperoxychloride, 5 g. zinc sulphide, are mixed intimately and thoroughlywith 25 g. of a water dispersion of polyvinylacetate, 0.5 g. of animalglue and 39.5

g. of water.

In order to prevent Peronospora on hops, the hops are sprayed with a0.5% suspension of the paste in water.

Experimental tests similar to those described in Example 1 were made ontwo adjacent ground parcels planted with hops. The hops on one groundparcel-was sprayed and the other left unsprayed. The hops in theuntreated ground parcel were severely attacked by Peronospora while thehops which were sprayed did not show any Peronospora attack and remainedhealthy.

Example 5 .-Spraying Paste The spray prepared according to Example 4 wastested on beets attacked by Cercospora. A test was made exactly asdescribed in Example 4 with the same results.

Example 6.-Spraying Powder [Proportions in grams] 20 g. of copperoxychloride, 5 g. zinc sulphide are mixed with 60 g. kaolin. Into thismix 5 g. of a higher molecular weight aromatic sulfonic acid, acting asa wetting and dispersion agent and 10 g. of powder acting as an adhesiveagent were worked, until complete homw geneity was obtained. A 0.30%suspension of this spraying powder in water was sprayed on apple treesduring the pre-blossoming period to prevent infestation withFusicladium. The effect when compared with trees which had not beensprayed was very marked.

To this spray insecticides were added, especially gammahexachlorocyclophexane and dichlordiphenyltrichlorethane.

Example 7.-Spraying Powder [Proportions in grams] 30 g. cuprous oxide, 5g. zinc sulphide are mixed with 45 g. of kaolin. Into this mix 5 g. ofhigh molecular weight aliphatic sulfonic acid such as sodiumsulforicinate and 10 g. of an adhesive known as cell powder and 5 g.hexachlorocyclohexane are worked.

2 kg. of this spraying powder are suspended in 600 liters of water andare sprayed over 1 hectare of ground with potato plants. Infection withPhytophthora was completely prevented. The Colorado potato beetle andits larvae were completely killed by the spraying.

Example '8.-Spray Powder 35 g. basic copper carbonate and 4 g. zincsulphide are mixed with 46 g. kaolin, 5 g. of a high molecular weightaliphatic sulfonic acid, as wetting and emulsifying agent, and 10 g.cellulose powder, as binding agent, are worked into the mixture.

3 kg. of the powder was dispersed in 600 liters of water and uniformlysprayed over one hectare of potato plants. Lots not sprayed developed aPhytophthora infection. 'Illhe sprayed lots remained healthy and free ofPhytopht ora.

Example 9.Spray Paste 30 g. basic copper carbonate and 5 g. zincchromate are stirred with 25 g. of an aqueous dispersion of polyvinylacetate, 0.5 g. lime powder as stabilizer and 39.5 g. water.

3 kg. of this pasty mass was disposed in 600 liters of water and sprayedover one hectare of potato plants. The effectiveness againstPhytophthora was the same as in Example 8.

Example 10.Spray Powder v 25 g. copper hydroxide and 5 g. zinc sulphideare mixed PF piwith 55 g. kaolin, g. of a high molecular weightaliphatic sulfonic acid, as wetting and emulsifying agent, and g.cellulose powder, as binding agent, are worked into the mixture.

Field experimentation, employing 3-6 kg. of this spray powder dispersedin 600 liters of water as a spray over one hectare of beets, producedinhibition of infection by Cercospora.

Example JL-Spray Paste 30 g. copper hydroxide and 5 g. zinc chromate arestirred with 25 g. of an aqueous dispersion of polyvinyl acetate, 0.5 g.lime powder as stabilizer and 39.5 g. water.

3 kg. of this pasty mass is dispersed in 600 liters of water and sprayedover one hectare of beets. The effectiveness against Cercospora was thesame as in Example 10.

This application is a continuation-in-part of Serial No. 547,303, filedNovember 16, 1955, now abandoned in favor of the present application.

What is claimed as new is as follows:

1. A mixture for protecting plants against fungicidal diseases such asPhytophthora, Fusicladium, Cercospora, and Peronospora comprising foreach 5 parts in weight of a zinc compound of the group consisting ofzinc sulphide and zinc chromate, between and 45 parts by Weight of aninsoluble fungicidal copper compound of the group consisting of cuprousoxide, copper hydroxide, copper oxychloride and basic copper carbonate;and from 3 to 12 parts by weight of kaolin.

2. A fungicidal mixture consisting essentially of 5 parts by weight ofZinc chromate and parts by Weight of copper oxychloride.

3. A fungicidal mixture consisting essentially of between 20 and partsby weight of copper oxychloride and about 5 parts by weight of Zincsulphide.

4. A fungicidal mixture consisting essentially of zinc sulphide andbasic copper carbonate in the relative proportions of about 1 part ofzinc sulfide to between 4 and 9 parts of basic copper carbonate, byweight.

5. A fungicidal mixture consisting essentially of zinc sulphide andcopper hydroxide in the relative proportions of about 1 part of zincsulfide to between about 4 and 9 parts of copper hydroxide, by weight.

6. The process of controlling fungus growth of a fungus selected fromthe group consisting of Phytophthora, Fusicladium, Cercospora, andPeronospora on living plants which comprises applying to the plant afungicidal composition having as an active ingredient a mixtureconsisting of a zinc compound selected from the group consisting of zincsulphide and Zinc chromate and a copper compound selected from the groupconsisting of cuprous oxide, copper hydroxide, copper oxychloride andbasic copper carbonate the relative proportions of said Zinc compoundand said copper compound being between about 4 and 9 parts by weight ofcopper compound for each part of weight of zinc compound.

7. The method of claim 6, wherein the mixture contains between 20 andparts by weight of copper compound for each 5 parts by weight of zinccompound.

8. The method of claim 6 wherein the zinc compound is zinc chromate andthe copper compound is copper oxychloride.

9. The method of claim 6 wherein the zinc compound is zinc sulphide andthe copper compound is copper oxychloride.

10. The method of claim 6 wherein the zinc compound is Zinc sulphide andthe copper compound is basic copper carbonate.

11. The method of claim 6 wherein the zinc compound is zinc sulphide andthe copper compound is copper hydroxide.

Frear: A Catalogue of Insecticides and Fungicides (1948), vol. 1, page173; vol. 2, pages 51, 52, 56.

6. THE PROCESS OF CONTROLLING FUNGUS GROWTH OF A FUNGAS SELECTED FROMTHE GROUP CONSISTING OF PHYTOPHTHORA, FUSICLADIUM, CERCOSPORA, ANDPERONOSPORA ON LIVING PLANTS WHICH COMPRISES APPLYING TO THE PLANT AFUNGICIDAL COMPOSITION HAVING AS AN ACTIVE INGREDIENT A MIXTURECONSISTING OF A ZINC COMPOUND SELECTED FROM THE GROUP CONSISTING OF ZINCSULPHIDE AND ZINC CHROMATE AND A COPPER COMPOUND SELECTED FROM THE GROUPCONSISTING OF CUPROUS OXIDE, COPPER HYDROXIDE, COPPER OCYCHLORIDE ANDBASIC COPPER CARBONATE THE RELATIVE PROPORTIONS OF SAID ZINC COMPOUNDAND SAID COPPER COMPOUND BEING BETWEEN ABOUT 4 AND 9 PARTS BY WEIGHT OFCOPPER COMPOUND FOR EACH PART OF WEIGHT OF ZINC COMPOUND.